Halogenated vat dyestuffs of the anthraquinone series and process of making same



Patented Aug. 10, 1926'.

UNI ED "STATES PATENT OFFICE.

ALFRED B0111, OF OFFENBACH-ON-THE-MAIN, GERMANY, ASSIGNOR TOT. G. BARBER mnnsrnm AKTIENGESELLSCHAIT, OF FRANKI'ORT, GERMANY.

mnoenmlrnn var nynsrnrrs oi:- rnn anrnaaanmofin SERIES annrnocnss or name SAME.

30 Drawing. Application filed June 9, 1925, Serial Ila-36,021, and in Germany .Tunc 1 924.

My invention relates to new halogenated vat dyestuffs of the anthraquinone series, which may be obtained by treating dyestufis of the pyrazole-anthrone-yellow se- I ries, i. e., pyrazole-anthrone-yellow and its N-alkyland N-aralkyl-derivatives such as mentioned in the U. S. Letters Patent No.

1,329,435 and the German Letters Patent 359,139, with halogens. Advautageously 1 the halogenation may be conducted while adding iodine and in a strong acid containing S0 such as oleum or chlorosulfonic acld.

The new dyestuflFs are when dry yello w to dark red powders, insoluble in organlc solvents, soluble in concentrated sulfuric acid to a bluish red solution, in oleum to a a reddish violet solution, yielding with alkaline hydrosulfite a blue vat and dyeing cotton in blue tones, whichupon exposure to wherein R designates a monovalent radical such as hydrogen or organic radicals.

up as usually.-

' The chlorinated derivatives of the pyrazole-anthrone-yellow'series are the most im portantbodies of this class. If certain published data are assumed to be correct, such chlorinated derivatives mlght be represented by the following general formula:

Cl; e

wherein R designates a monovalent radical such as hydrogen or organic radicals.

The following examples illustrate the nature of the invention, the parts being by weight. Example 1.

100 parts of pyrazole-anthrone-yellow are dissolved'in 1000 parts of oleum of 25% strength, 0,5 parts of finely powdered iodine are strewn in and at-about C; a moderate current of chlorine is introduced for about 12 hours, until the quantity of chloline, which is sufliclent for a dichlorinated derivative, is absorbed. The mass is worked 0 The dichloropyrazole anthrone yellow, thus formed, is when dry an orange powder, soluble in sulfuric acid to a red solution. It yields a blue vat and dyes cotton in orange shades of an excellent fastness. This dichloro pyrazole anthrone yellow might be represented by the following for-,

mula (assuming the correctness data found in scientific literature):

Example 2.

100 parts of the dyestufi, prepared 'according to example 3 of the U. S. Letters Patent No. 1,329,435 are dissolved in 1000 parts of oleum, containing 20% .of S0,

About 0.05 to 0.5 parts of finely powdered iodine are strewn in and at about 50 C.

while stirring rapidly armoderate current of chlorine is introduced in the solution, until the quantity of chlorine corresponding to a dichloro-derivative, is absorbed. The chlorinated derivative, thus formed, being probably a dichloro-N-diethylpyrazole-anthrone-yellow, yields from a blue vat a clear bluish red of an excellent fast-- ness upon cotton. This chlorinated derivative might be represented bythe following formula (assuming the correctness of certain data found in scientific literature) By varying the period of introducing chlorine also other chlorinated derivatives may be obtained. In a similarmanner also other dyestufis of the pyrazole-anthroneyellow series may be treated with chlorine and bromine.

Now what I claim and desire to secure by Letters Patent is the following:

1. A process of making new halogenated vat dyestuffs of the anthraquinone series consisting in treating dyestuffs of the pyrazole-anthrone-yellow series, mentioned in the U. S. Letters Patent No. 1,329,435 and the German Letters Patent No. 359,139, with halogens.

2. A process of making new halogenated vat dyestufl's of theanthraquinone series consisting in treating dyestufls of the pyrazole-anthrone-yellow series, mentioned in theU. S. Letters Patent No. 1,329,435 and the German Letters Patent No. 359,139,

of certain with halogens while adding iodine and in a strong acid containing S0 3. As new articles'halogenated vat dyestuffs of the anthraquinone series, which are halogenated derivatives of the dyestufis of the" pyrazole-anthrone-yellow series, mentioned in the U. S. Letters Patent No. 1,329,435 and the German Letters Patent No. 359,139, which halogenated derivatives may perhaps be represented by the general formula l wherein R designates a monovalent radical, and which are when dry yellow to dark red powders, insoluble in organic solvents, solu ble in concentrated sulfuric acid to a bluish red solution, in oleum to a, reddish violet solution, yielding with alkaline hydrosulfite a blue vat and dyeing cotton in blue tones, which upon exposure to the air are changed into yellow to bluish red shades of an es ecial fastness to boiling water.

4., process of making new chlorinated vat dyestuffs of the anthraquinone series consisting in treating dyestuifs of the pyrazole-anthrone-yellow series, mentioned in the U. S. Letters Patent No. 1,329,435 and the German Letters Patent No. 359,139, with chlorine. i

5. A process of making new chlorinated vat dyestuffs of the anthraquinone seri consisting in treating dyestuffs of the pyrazole-anthrone-yellow series, mentioned in the U. S. Letters Patent No. 1,329,435 and the German Letters Patent No. 359,139, with chlorine while adding iodine and in a strong acid containing S0 6. As new articles chlorinated vat dyestuifs of the 'anthraquinone series, which are chlorinated derivatives of the dyestuffs of the pyrazole-anthrone-yellow' series, mentioned 'in the U. S. Letters Patent No.

1,329,435 359,139, perhaps mula and the German Letters Patent No. which chlorinated derivatives may be represented by the general forcial fa'stness to boiling water.

wherein R designates a monovalent radical, and which are when dry yellow 't 'dark red powders, insoluble'in organic solvents, soluble in concentrated sulfuric acid to a bluish red solution, .in oleum to a reddish violet solution, yielding with alkaline hydrosulfite a blue vat and dyeing cotton in blue tones, which upon exposure to the air are changed into yellow to bluish red shades of an espe- 7, A process of. making anew chlorinated vat dyestuff of the anthraquinone series, consisting in treating-the N-diethylderivative of pyrazole-anthrone-yellow with chlorlne.

8. A process of making a new chlorinated vat dyestutf of the anthraquinone series, consisting in treating the i -diethylderivative of pyrazole-anthrone-yellow with chlorine while adding iodine and in a strong acid, containing SO p 9. As a new article a chlorinated vat dyestufi' of the anthraquinone series being probably dichloro-N-diethyl-pyrazole-anthroneyellow, which may perhaps be represented by the formula and which is when dry a bluish red powder, 7

insoluble in organic solvents, soluble in concentrated sulfuric acid to a bluish red solution, in oleum to a reddish violet solution, yielding with alkaline hydrosulfite a blue vat and dyeng cotton in blue tones, which upon exposure to the air are changed into a bluish red of an especial fastness to boiling water.

In testimony, that I claim the foregoing as my invention, I have signed my name, this 28th day of May, 1925.

ALFRED HOLL. 

